U.S. patent number 4,780,457 [Application Number 07/079,865] was granted by the patent office on 1988-10-25 for insecticidal composition for agricultural and horticultural use.
This patent grant is currently assigned to Nihon Tokushi Noyaku Seizo K.K.. Invention is credited to Yumi Hattori, Shoko Sasaki, Shinichi Tsuboi.
United States Patent |
4,780,457 |
Tsuboi , et al. |
October 25, 1988 |
**Please see images for:
( Certificate of Correction ) ** |
Insecticidal composition for agricultural and horticultural use
Abstract
A synergistic insecticidal composition comprising a
nitromethylene derivative of the formula ##STR1## in which X is a
lower alkyl group, a lower alkoxy group or a halogen atom, n is 0,
1 or 2, and m is 2 or 3, and an insecticide which is a carboxylic
acid ester, carbamate, organophosphate ester or one of a group of
specific compounds.
Inventors: |
Tsuboi; Shinichi (Tokyo,
JP), Sasaki; Shoko (Tokyo, JP), Hattori;
Yumi (Tokyo, JP) |
Assignee: |
Nihon Tokushi Noyaku Seizo K.K.
(Tokyo, JP)
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Family
ID: |
27475734 |
Appl.
No.: |
07/079,865 |
Filed: |
July 30, 1987 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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904087 |
Sep 4, 1986 |
4725589 |
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Foreign Application Priority Data
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Sep 5, 1985 [JP] |
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60-194919 |
Sep 5, 1985 [JP] |
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60-194920 |
Sep 5, 1985 [JP] |
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60-194921 |
Sep 6, 1985 [JP] |
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60-195980 |
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Current U.S.
Class: |
514/89; 514/341;
514/256 |
Current CPC
Class: |
A01N
43/50 (20130101); A01N 43/54 (20130101); A01N
43/50 (20130101); A01N 2300/00 (20130101); A01N
43/54 (20130101); A01N 2300/00 (20130101) |
Current International
Class: |
A01N
43/48 (20060101); A01N 43/50 (20060101); A01N
43/54 (20060101); A01N 043/40 (); A01N 043/54 ();
A01N 057/00 () |
Field of
Search: |
;514/89,256,341 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Australian Patent Abst. AU-A-41097/85 (4/12/85)..
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Primary Examiner: Robinson; Allen J.
Attorney, Agent or Firm: Sprung Horn Kramer & Woods
Parent Case Text
This is a division of application Ser. No. 904,087, filed Sept. 4,
1986, now U.S. Pat. No. 4,725,589.
Claims
We claim:
1. An inseciticidal composition comprising an insecticidally
effective amount of (1) a nitromethylene derivative of the formula
##STR11## in which X is a lower alkyl group, a lower alkoxy group
or a halogen atom,
n is 0, 1 or 1, and
m is 2 or 3, and
(2) is chlorpyrifos methyl or chlorpyrifos, wherein the ratio of
the nitromethylene derivative to chlorpyrifos methyl is 1:1 to 5:1
or wherein the ratio of the nitromethylene derivative to
chlorpyrifos is 1:1.
2. A composition according to claim 1 wherein the second ingredient
is chlorpyrifos methyl.
3. A method of combating insects which comprises applying to such
insects or to an insect habitat an insecticidally effective amount
of a composition according to claim 1.
Description
The present invention relates to novel insecticidal synergistic
active substance combinations of known nitromethylene derivatives
and known insecticides.
Nitromehylene derivatives and their use as insecticides have
already been disclosed in Japanese patent application Nos.
20620/1984, 72966/1984 and 132943/1984.
It has already been disclosed that the following insecticides have
insecticidal activity: S,S'-2-dimethylaminotrimethylene
bis(thiocarbamate), N,N-dimethyl-1,2,3-trithian-4-ylamine,
2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazinan-4-one and
1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea (The Pesticide
Manual, 7th edition, 1983 published by the British Crop Protection
Council),
N-(2,6-di-fluorobenzoyl)-N'-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-
pyridyloxy)phenyl]urea (Japanese patent publication No.
53786/1982), and 3-phenoxy benzyl
2-(4-ethoxyphenyl)-2-methylpropylether (Japanese laid open patent
application No. 72928/1982).
However, the activities of these known insecticidal compounds are
not entirely satisfactory especially when the concentrations of
these active compounds are low and when they are used only in small
amounts.
It was furthermore already been disclosed that the following
carboxylic acid esters have insecticidal activity: for example,
.alpha.-cyano-5-phenoxy-4-fluoro-benzyl
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (Japanese
patent publication No. 57025/1982),
(RS)-.alpha.-cyano-3-phenoxybenzyl
(Z)-(1RS,3RS)-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropanec
arboxylate,
(RS)-.alpha.-cyano-3-phenoxy-benzyl-2,2,3,3-tetramethylcyclopropanecarboxy
late, (RS)-.alpha.-cyano-3-phenoxybenzyl
(RS)-2-(4-chlorophenyl)-3-methylbutyrate, and
.alpha.-cyano-3-phenoxybenzyl
1-p-ethoxyphenyl-2,2-dichlorocyclopropane-1- carboxylate (see the
Pesticide Manual, 7th Edition, 1983, published by the British Crop
Protection Council).
However, the activities of these known insecticidal compounds are
not entirely satisfactory when their concentrations as active
compounds are low or when they are applied only in small
amounts.
It has furthermore already been disclosed that the following
carbamates have insecticidal activity, for example,
2-isopropoxyphenyl methylcarbamate, 2-sec-butylphenyl
methylcarbamate, m-tolyl methylcarbamate, 3,4-xylyl
methylcarbamate, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl
methylcarbamate, .alpha.-ethylthio-o-tolyl methylcarbamate, and
2-dimethylamino-5,6-dimethylcarbamate [see The Pesticide Manual,
7th edition, 1983 (published by the British Crop Protection
Council].
However, the activity of these known carbamates is not necessarily
satisfactory when their concentration is low or they are applied
only in small amounts. Moreover, as a result of using these
insecticides over several yeas, some insects have gained resistance
to some of these insecticides and these insects have become very
difficult to control.
It has furthermore been disclosed that the following
organophosphate esters have insecticidal activity: for example,
O-ethyl O-4-methylthiophenyl S-propyl phosphorodithioate,
O-2,4-dichlorophenyl O-ethyl S-propyl phosphorodiothioate,
O,O-diethyl O-5-phenylisoxazol-3-yl phosphorothioate,
2,3-dihydro-3-oxo-2-phenyl-6-pyridazinyl diethyl
phosphorothioate,
O,S-dimethyl acetylphosphoramidothioate,
O,O-diethyl S-2-ethylthioethyl phosphorodithioate, and
O,O-dimethyl S-2-(1-methylcarbamoylethylthio) ethyl
phosphorothioate (see The Pesticidal Manual, 7th Edition, 1983,
published by the British Crop Protection Council).
However, the activity of these known organo-phosphates is not
necessarily satisfactory when their concentrations are low or they
are applied only in small amounts. Furthermore, as a result of
using these insecticides over several years, some pests have
acquired resistance to some of these chemicals, and it has become
extremely difficult to control these pests.
It has been found that novel active substance combinations of (1) a
nitromethylene derivative represented by the formula (I) ##STR2##
wherein X represents a lower alkyl group, a lower alkoxy group or a
halogen atom, n represents 0, 1 or 2, and m represents 2 or 3, and
at least one insecticidal compound selected from one of the
following groups (2) to (5):
(2) group of insecticides consisting of
S,S'-2-dimethylaminotrimethylene bis(thiocarbamate),
N,N-dimethyl-1,2,3-trithian-5-ylamine,
2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazinan-4-one,
1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea,
N-(2,6-difluorobenzoyl)-N'[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-py
ridyloxy)-phenyl]urea, 3-phenoxybenzyl
2-(4-ethoxyphenyl)-2-methylpropylether,
1-(4-trifluoromethoxy-phenyl)-3-(2-chlorobenzoyl)urea,
1-(4-(2-dichloro-1-difluoro-ethoxy)phenyl-3-(2-chlorobenzoyl)urea,
1-(4-trifluorophenyl)-3-(2,6-difluorobenzoyl)urea,
1-(2,4-difluoro-3,5-dichloro-phenyl)-3-(2,6-difluorobenzoyl)urea,
and
N-[6-(2,2,3-trifluoro-3-chloro-benzodioxin-(1,4))]-N'-(2,6-difluorobenzoyl
)urea,
(3) group of carboxylic acid esters of the following formula
##STR3## wherein R.sup.1 represents a substituted lower alkyl group
or a substituted cyclopropyl group, R.sup.2 represents a hydrogen
atom or CN, and each of X.sup.1 and X.sup.2 represents a hydrogen
or halogen atom,
(4) group of carbamates of the following formula ##STR4## wherein
R.sup.3 represents a substituted or unsubstituted aryl group,
heterocyclic group or oxime group, R.sup.4 represents a hydrogen
atom or a lower alkyl group, and R.sup.5 represents a lower alkyl
group or the group ##STR5## in which R.sup.6 represents a lower
alkyl group, and R.sup.7 represents a lower alkyl group, a lower
alkoxycarbonyl group or a lower alkoxycarbonyl alkyl group,
(5) group of organophosphate esters of the following formula
##STR6## wherein X.sup.3 represents an oxygen or sulfur atom,
X.sup.4 represents an oxygen or sulfur atom, or a direct bond
between the phosphorus atom and R.sup.10 in the formula, R.sup.8
represents a lower alkyl group, R.sup.9 represents a lower alkoxy
group, a lower alkylthio groups, a lower alkylcarbonylamide group
or a phenyl group, and R.sup.10 represents a substituted or
unsubstituted lower alkyl, lower alkenyl, phenyl or heteroaryl
group, or R.sup.9 and R.sup.10 together represent a phosphorine
ring together with the phosphorus atom and X.sup.4 in the formula,
exhibit a particular high insecticidal activity.
Surprisingly, the insecticidal activity of the active substance
combinations according to the invention is substantially greater
than the sum of the effects of the individual active substances.
Accordingly, a genuine synergistic effect is present.
By applying the active substance combinations according to the
invention, one can achieve a cooperative and synergistic effect
against paddy pests such as hemipterous plant hoppers (e.g.,
white-backed planthopper) and lepidopterous paddy leaf roller and
pests on horticultural crops including fruits and vegetables, such
as lepidopterous diamondback moths in lower concentrations than the
active compound applied individually, and furthermore a residual
effect, can be detected.
The insecticidal composition of this invention therefore provides a
technical advantage which is very effective in the cultivation of
agricultural and horticultural crops and is of outstanding
industrial utility and applicability.
The nitromethylene derivatives of general formula (I) used in the
active substance combinations according to the invention are
defined by the following formula ##STR7## wherein X represents a
lower alkyl group, a lower alkoxy group, or a halogen atom, n
represents 0, 1 or 2 and m represents 2 or 3.
In formula (I), preferably, X represents a methyl group, a methoxy
group, a chlorine atom, a bromine atom or a fluorine atom, p
represents 1 or 2, m represents 2 or 3, and the bonding position on
the pyridine ring is 3- (or 5-).
The nitromethylene derivatives of general formula (I) can exist
also in the form of salts. Examples of the salts include inorganic
acid salts, sulfonic acid salts, organic acid salts and metal
salts, preferably hydrochlorides, p-toluenesulfonates, cupric
acetates, and succinates. Accordingly, the nitromethylene
derivatives of formula (I), as used herein, denote their salts as
well.
Examples of the nitromethylene derivatives of the formula (I) used
in the active substance combination according to the invention
include
1-(3-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine,
1-(2-methyl-5-pyridylmethyl)-2-(nitromethylene)imidazolidine,
1-(2-methyl-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine,
1-(2-methoxy-5-pyridylmethyl)-2-(nitromethylene)imidazolidine,
1-(2-methoxy-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimdine,
1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine,
1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyimidine,
1-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine,
1-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimdine,
1-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)imidazolidine,
1-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine,
1-(5-chloro-2-pyridylmethyl)-2-(nitromethylene)imidazolidine,
1-(5-chloro-2-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine,
1-(2,4-dichloro-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine,
1-(2,4-dibromo-5-pyridylmethyl)-2-(nitromethylene)imidazolidine,
1-(2,3-dichloro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine,
1-(3-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine
hydrochloride,
1-(2-methyl-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine
p-toluenesulfonate,
1-(2-methoxy-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimdine
succinate,
1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine
hydrochloride,
1-(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine
cupric acetate,
1-(2-bromo-5-pyridylmethyl)-2-(nitromethylene)imidazolidine
succinate, and
1-(2,4-dichloro-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine
p-toluenesulfonate.
The insecticidal activity of the nitromethylene derivatives of
general formula (I) is described in Japanese patent application
Nos. 26020/1984, 72966/1984 and 13294371984.
Examples of the known insecticides of the other component selected
from group (2) above are as follows:
S,S'-2-dimethylaminotrimethylene bis(thiocarbamate) (cartap),
N,N-dimethyl-1,2,3-trithian-5-ylamine (thiocyclam),
2-(tert-butylimino-3-iso-propyl-5-phenyl-1,3,5-thiadiazinan-4-one
(buprofezin), 1-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea
(difluorozuron) (The Pesticide Manual, 7th edition, 1983 published
by the British Crop Protection Council).
N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-py
ridyloxy)phenyl]urea (Japanese Patent Publication No. 53786(1982),
and 3-phenoxybenzyl 2-(4-ethoxyphenyl)-2-methyl-propylether
(Japanese Laid Open Application No. 72928/1982).
Preferred carboxylic acid esters (group (3)) of the formula (II)
used in the active substance combinations according to the
invention are those of the general formula (II) in which
R.sup.1 represents an alkyl group substituted by a phenyl group
which is substituted by a substituent selected from halogen atoms,
lower alkoxy groups and lower haloalkoxy groups, and the alkyl
group may further be substituted by a dichlorocyclopropane group,
or
R.sup.1 represents an alkyl group substituted by a phenylamino
group which is substituted by a halogen atom and/or haloalkyl
group, the preferred haloalkyl group being a trifluoromethyl group,
or
R.sup.1 represents a cyclopropyl group substituted by an alkyl
group having 1 to 3 carbon atoms, preferably a methyl group, or a
cyclopropyl group substituted by an alkyl group having 1 to 3
carbon atoms, preferably a methyl group, and a halogenoalkenyl
group having 2 to 3 carbon atoms;
R.sup.2 represents a hydrogen atom or CN; and each of X.sup.1 and
X.sup.2 represents a hydrogen atom, a chlorine atom or a fluorine
atom, preferably X.sup.1 represents a hydrogen or fluorine atom,
and X.sup.2 represents a hydrogen atom.
Examples of the carboxylic acid esters of general formula (II)
include
.alpha.-cyano-5-phenoxy-4-fluoro-benzyl(3-(2,2-dichlorovinyl)-2,2-dimethylc
yclopropanecarboxylate (cyfluthrin),
3-phenoxybenzyl(1RS,3RS;1RS,3RS)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopro
panecarboxylate (permethrin,
(RS)-.alpha.-cyano-3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2
,2-dimethylcyclopropanecarboxylate (cypermethrin),
(S)-.alpha.-cyano-3-phenoxybenzyl(1R,3R)-3-(2,2-di-bromovinyl)-2,2-dimethyl
cyclopropanecarboxylate (deltamethrin),
(RS)-.alpha.-cyano-3-phenoxybenzyl(Z)-(1RS,3RS)-(-2-chloro-3,3,3-trifluorop
ropenyl)-2,2-dimethylcyclopropanecarboxylate (cyhalothrin),
(RS)-.alpha.-cyano-3-phenoxybenzyl
2,2,3,3-tetramethylcyclopropanecarboxylate (fenpropathrin),
(RS)-.alpha.-cyano-3-phenoxybenzyl(RS)-2-(4-chlorophenyl)-3-methylbutyrate
(fenvalerate),
(RS)-.alpha.-cyano-3-phenoxybenzyl(S)-2-(4-difluoromethoxyphenyl)-3-methylb
utyrate (flucythrinate),
.alpha.-cyano-3-phenoxybenzyl
1-p-ethoxyphenyl-2,2-dichlorocyclopropan-1-carboxylate, and
(RS)-.alpha.-cyano-3-phenoxybenzyl
N-(2-chloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)-D-valinate
(fluvalinate).
The carboxylic acid esters as one component of the active substance
combinations according to the invention have already been known.
For example, they are described as insecticides in The Pesticide
Manual, 7th Edition, 1983, published by The British Crop Protection
Council.
Preferred carbamates (group (4)) are those of general formula (III)
in which R.sup.3 represents a phenyl group substituted by one or
two same or different alkyl groups, alkoxy groups having 1 to 4
carbon atoms or ethylthiomethyl groups; or R.sup.3 represents a
naphthyl group, a pyrimidinyl group substituted by a dialkylamino
group having 1 to 3 carbon atoms, preferably a dimethylamino group
and two alkyl groups having 1 to 4 carbon atoms, preferably methyl
groups, or a 2,3-dihydrobenzofuranyl or benzoxazolyl group
substituted by an alkyl group having 1 to 4 carbon atoms,
preferably a methyl group; or R.sup.3 represents a group of the
general formula ##STR8## in which R.sup.11 represents an alkyl
group having 1 to 4 carbon atoms, preferably a methyl group, and
R.sup.12 represents an alkylthio group having 1 to 4 carbon atoms,
preferably a methylthio group; R.sup.4 represents a hydrogen atom
or an alkyl group having 1 to 4 carbon atoms, preferred alkyl group
having 1 to 4 carbon atoms of R.sup.4 represents a methyl group;
and R.sup.5 represents an alkyl group having 1 to 4 carbon atoms,
preferably a methyl group, or a group of the formula ##STR9## in
which R.sup.6 represents an alkyl group having 1 to 5 carbon atoms,
and R.sup.7 represents an alkyl group, an alkoxycarbonyl group or
an alkoxycarbonylalkyl group, each having 1 to 5 carbon atoms.
Examples of the carbamates of general formula (III) include
2-isopropoxyphenyl methylcarbamate (propoxur),
o-cumenyl methylcarbamate (isoprocarb),
2-sec-butylphenyl methylcarbamate (BPMC),
3,4-xylyl methylcarbamate (xylylcarb),
m-tolyl methylcarbamate (metolcarb),
3,5-xylyl methylcarbamate (XMC),
.alpha.-ethylthio-o-tolyl methylcarbamate (ethiofencarb),
1-naphthyl methylcarbamate (carbaryl),
2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate
(pirimicarb),
2,2-dimethyl-1,3-benzodioxol-4-yl methylcarbamate (bendiocarb),
2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate
(carbofuran),
butyl 2,3-dihydro-2,2-dimethylbenzofuran-7-yl
N,N-dimethyl-N,N-thiodicarbamate (furanthiocarb),
2,3-dihydro-2,2-dimethylbenzofuran-7-yl(dibutyl)aminosulfenyl)(methyl)carba
mate (carbosulfan) (See Japanese patent publication No.
39487/1983),
2,3-dihydro-2,2-dimethylbenzofuran-7-yl
N-(N-isopropyl-N-ethoxycarbonylethylaminosulfenyl)-N-methylcarbamate
(aminosulfulan) (See Japanese patent laid open application No.
200377/1982), and
S-methyl N-(methylcarbamoyloxy)thioacetimidate (methomyl).
The carbamates used as one component of the active substance
combinations according to the invention are already known. For
example, they are described in The Pesticide Manual, 7th edition,
1983 (published by The British Crop Protection Council).
Preferred organophosphate esters (group (5)) are those of the
general formula (IV) in which
R.sup.8 represents an alkyl group having 1 to 4 carbon atoms,
R.sup.9 represents an alkoxy group, an alkylthio group, an
alkylcarbonylamide group, each having 1 to 4 carbon atoms, or a
phenyl group,
R.sup.10 represents a phenyl group substituted by one or two
substituents selected from halogen atoms and methyl, methylthio,
nitro and cyano groups, or
R.sup.10 represents an alkyl group having 1 to 3 carbon atom which
may optionally be substituted by a halogen atom, an alkylthio (or
sulfinyl) group having 2 to 3 carbon atoms, a phenyl group, an
alkoxycarbonyl group having 1 to 4 carbon atoms, an alkylcarbamoyl
group having 1 to 4 carbon atoms, an
alkylcarbamoylalkyl(C.sub.1-2)thioalkyl C(.sub.1-2) group or an
alkoxycarbonyl-N-methylcarbamoyl group having 1 to 4 carbon atoms,
a halogen-substituted benzoxazole group, or an alkyl group having 1
to 2 carbon atoms substituted by a halogen atom and a phthalimide
group, or
R.sup.10 represents an alkenyl group having 2 to 3 carbon atoms
substituted by one or two substituents selected from halogen atoms,
halogen sustituted phenyl group and alkylcarbamoyl group, or
R.sup.10 represents a pyridinyl, pyrimidinyl, pyridazinyl,
quinoxalinyl, isoxazolyl or oxo-1,3,4-thiadiazolyl group
substituted by 1 to 3 same or different alkyl groups, alkoxy
groups, dialkylamino groups, each having 1 to 4 carbon atoms,
halogen atoms, or phenyl groups, or
R.sup.9 and R.sup.10 together represent a benzodioxaphosphorine
ring, or
when X.sub.4 represents a direct bond between the phosphorus atom
and R.sup.10, R.sup.10 represents the group ##STR10##
Examples of the organophosphates of general formula (IV) are
O,O-dimethyl O-4-methylthio-m-tolyl phosphorothioate
(fenthion),
O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate (fenitrothion),
4-(methylthio)phenyl dipropyl phosphate (propaphos),
O-4-cyanophenyl O,O-dimethyl phosphorothioate (cyanophos),
O,2,4-dichlorophenyl O-ethyl S-propyl phosphorodithioate
(prothiofos),
O-ethyl O-4-methylthiophenyl S-propyl phosphorodithioate
(sulprofos),
O-4-bromo-2-chlorphenyl O-ethyl S-propyl phosphorothioate
(profenofos),
O-ethyl O-4-nitrophenyl phenylphosphonothioate (EPN),
O-4-cyanophenyl O-ethyl phenylphosphonothioate (cyanofenphos),
O,S-dimethyl acetylphosphoramidothioate (acephate),
S-2-ethylsulfinyl-1-methylethyl O,O-dimethyl phosphorothioate
(oxydeprofos),
O,O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfoton),
S-2-ethylthioethyl O,O-dimethyl phosphorodithioate (thiometon),
S-.alpha.-ethoxycarbonylbenzyl O,O-dimethyl phosphorodithioate
(phenthoate),
S-1,2-bis(ethoxycarbonyl)ethyl O,O-dimethyl phosphorodithioate
(malathion),
O,O-dimethyl S-methylcarbamoylmethyl phosphorodithioate
(dimethoate),
O,O-dimethyl S-S-(1-methylcarbamoylethylthio)ethyl phosphorothioate
(vamidothion),
S-(N-ethoxycarbonyl-N-methylcarbamoylmethyl) O,O-diethyl
phosphorodithioate (mecarbam),
dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate
(trichlorphon),
1,2-dibromo-2,2-dichloroethyl dimethyl phosphate (naled),
2,2-dichlorovinyl dimethyl phosphate (dichlorvos),
2-chloro-1-(2,4-dichlorophenyl)vinyl diethyl phosphate
(chlorofenvinphos),
(Z)-2-chloro-1-(2,4,5-trichlorophenyl)vinyl dimethyl phosphate
(tetrachlorvinphos),
dimethyl (E)-1-methyl-2-(methylcarbamoyl)vinyl phosphate
(monocrotophos),
S-6-chloro-2,3-dihydro-2-oxobenzoxazol-3-ylmethyl O,O-diethyl
phosphorodithioate (phosalone),
S-2-chloro-1-phthalimidoethyl O,O-diethyl phosphorodithioate
(dialifos),
O,O-dimethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate
(chlorpyrifos-methyl),
O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate
(chlorpyrifos),
O-2-diethylamino-6-methylpyrimidin-4-yl, O,O-dimethyl
phosphorothioate (pirimophos-methyl),
O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate
(diazinon),
O-6-ethoxy-2-ethylpyrimidin-4-yl O,O-dimethyl phosphorothioate
(etrimfos),
2,3-dihydro-3-oxo-2-phenyl-6-pyridazinyl diethyl phosphorothioate
(pyridaphenthion),
O,O-diethyl O-quinoxalin-2-yl phosphorothioate (quinalphos),
O,O-diethyl O-5-phenylisoxazol-3-yl phosphorothioate
(isoxathion),
S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiaziazol-3-ylmethyl
O,O-dimethyl phosphorodithioate (methidathion), and
2-methoxy-4H-1,3,2.lambda..sup.5 -benzodioxaphosphorine-2-sulfide
(salithion).
The organophosphate esters, one component of the active substance
combinations according to the invention, are already known, and are
described, for example, in The Pesticide Manual, 7th edition, 1983
(published by The British Crop Protection Council) as
inseciticides.
Among the above organophosphates, quinalphos, fenthion, sulprofos,
phenthoate, fenitrothion, diazinon, isoxathion, pyridaphenthion,
trichlorphon, chlorpyrifosmethyl, malathion, monocrotophos,
propaphos, EPN, etrimfos and tetrachlorvinphos, for example, are
used preferably for the control of lepidoptereous pests in paddies,
such as paddy leaf roller (Cnaphalocrocis medinalis) and rice stem
borer (Chilo suppressalis).
Prothiofos, sulprofos, dichlorovos, trichlorphon, cyanophos,
pyrimophos-methyl, chloropyrifos, dimethoate, phosalone,
methidathion, chlorofenvinphos, acephate, salithion, dialifos,
mecarbam, profenofos, naled, phenthoate, fenitrothion, diazinon,
isoxathion, malathion, EPN and cyanofenphos, for example, are used
preferably for the control of lepidoptereous pests in horticulture
such as diamonback moths (Plutella m culipennis), cabbage armyworms
(Mamestra brassicae) and leaf rollers.
Furthermore, disulfoton, vamidothion, thiometon and oxydeprofos,
for example, are used preferably for horticulture, especially for
controlling hemipterous pests such as aphids including aphids on
peach, cotton and apple.
The weight ratios of the groups of active substances in the active
substance combinations can vary within relative wide ranges. In
general, 0.05 to 10 parts by weight of active substance of the
group of active substances (2), preferably 0.1 to 5 parts by
weight, are used per part by weight of active substance of the
group of active substances (1).
Furthermore in general, 0.05 to 10 parts by weight of active
substance of the group of active substance (3) (carboxylic acid
esters of formula (II)), preferably 0.1 to 5 parts by weight, are
used per part by weight of active substance of the group of active
substances (1).
Furthermore in general, 0.1 to 20 parts by weight of active
substance of the group of active substances (4) (carbamates of
general formula (III)), preferably 0.2 to 15 parts by weight, are
used per part by weight of active substance of the group of active
substances (1).
Furthermore in general, 0.05 to 10 parts by weight of active
substance to the group of active substances (5) (organophosphate
esters of formula (IV)), preferably 0.1 to 5 parts by weight, are
used per part by weight of active substance of the group of active
substances (1).
The active substance combinations according to the invention
exhibit an excellent insecticidal activity. Hence, the active
substance combinations can be used as an insecticide by foliar
application, underwater or water surface application, soil
application, soil mixing treatment, application to nursery box,
etc.
The active substance combinations according to the invention show
strong insecticidal activity and therefore can be used as an
insecticide. The active substance combinations according to the
invention have no phytotoxicity to cultivated plants and low
toxicity to warm-blooded animals, and can be used to accurately
control pests, particularly insects, in agriculture and forestry,
and in protecting stored crops and products. They are active
against sensitive and resistant species and against all or some
stages of development.
For example, the active substance combinations according to the
invention can be effectively used to control paddy pests, for
example hemipterous plant hoppers (such as brown planthopper,
white-backed planthopper and smaller brown planthopper) and
leafhoppers, lepidopterous larvae (rice stem borer, paddy leaf
rolle, etc.), and coleopterous rice plant weevil, and pests on
horticultural crops such as fruit trees and vegetables, for example
lepidopterous larvae (diamondback moth, armyworms, leaf roller,
etc.) and hemipterous scales and aphids.
The active substance combinations according to the invention
exhibit powerful insecticidal effects. They can therefore be used
against the following pests.
______________________________________ Coleopterous insects
Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneum,
Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala
rufocuprea, Leptinotarsa decemkineata, Diabrotica spp., Monochamus
alternatus, Lissorhoptrus, oryzophilus, and Lyctus bruneus.
Lepidopterous insects Lymantria dispar, Malacosoma neustria, Pieris
rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis,
Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa
pomonella, Agrotis fucosa, Galleria mellonella, Plutella
maculipennis, Heliothis virscens, and Phyllocnistis citrella.
Hemipterous insects Nephotettix cincticeps, Nilaparvata lugens,
Laodelphax striatellus, Sogatella furcifera, Pseudococcus
comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis
gossypii, Ropalosiphum pseudobrassicae, Stephanitris nashi, Nezara
spp., Trialeurodes vaporariorum, and Psylla spp. Orthopterous
insects Gryllotalpa afticana and Locusta migratoria migratoriodes.
______________________________________
The active substance combinations can be converted into the
customary formulations, such as solutions, emulsions, suspensions,
powders, foams, pastes, granules, aerosols, natural and synthetic
materials impregnated with active compound, very fine capsules in
polymeric substances, coating compositions for use on seed, and
formulations used with burning equipment, such as fumigating
cartridges, fumigating cans and fumigating coils, as well as ULV
cold mist and warm mist formulations.
These formulations may be produced in known manner, for example by
mixing the active substance combinations with extenders, that is to
say liquid or liquefied gaseous or solid diluents or carriers,
optionally with the use of surface-active agents, that is to say
emulsifying agents and/or dispersing agents and/or foam-forming
agents. In the case of the use of water as an extender, organic
solvents can, for example, also be used as auxiliary solvents.
As liquid solvents diluents or carriers, there are suitable in the
main, aromatic hydrocarbons, such as xylene, toluene or alkyl
naphthalene, chlorinated aromatic or chlorinated aliphatic
hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene
chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins,
for example mineral oil fractions, alcohols, such as butanol or
glycol as well as their ethers and esters, ketones, such as
acetone, methyl ethyl ketone, methyl isobutyl ketone or
cyclohexanone, or strongly polar solvents, such as
dimethylformamide and dimethyl-sulphoxide, as well as water.
By liquefied gaseous diluents or carriers are meant liquids which
would be gaseous at normal temperature and under normal pressure,
for example aerosol propellants, such as halogenated hydrocarbons
as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such
as kaolins, clays, talc, chalk, quartz, attapulgite,
montmorillonite or diatomaceous earth, and ground synthetic
minerals, such as highly-dispersed silicic acid, alumina and
silicates. As solid carriers for granules there may be used crushed
and fractionated natural rocks such as calcite, marble, pumice,
sepiolite and dolomite, as well as synthetic granules of inorganic
and organic meals, and granules of organic material such as
sawdust, coconut shells, corn cobs and tobacco stalks.
As emulsifying and/or foam-forming agent there may be used
non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty
acid esters, polyoxyethylene-fatty alcohol ethers, for example,
alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates,
aryl sulphonates as well as albumin hydrolysis products. Dispersing
agents include, for example, lignin sulphite waste liquors and
methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic
polymers in the form of powders, granules or latices, such as gum
arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the
formulation.
It is possible to use colorants such as inorganic pigments, for
example iron oxide, titanium oxide and Prussian Blue, and organic
dyestuffs, such as alizarin dyestuffs, azo dyestufs or metal
phthalocyanine dyestuffs, and trace nutrients, such as salts of
iron, manganese boron, copper, cobalt, molybdenum and zinc.
The formulations in general in general contain from 0.1 to 95
percent by weight of active compound, preferably from 0.5 to 90
percent by weight.
The active substance combinations according to the invention can be
present in their commercially available formulations and in the use
forms, prepared from these formulations, as a mixture with other
active compounds, such as insecticides, baits, sterilizing agents,
acaricides, nematicides, fungicides, growth-regulating substances
or herbicides. The insecticides include, for example, phosphates,
carbamates, carboxylates, chlorinates hydrocarbons, phenylureas,
and substances produced by microorganisms.
The active substance combinations according to the invention can
furthermore be present in their commercially available formulations
and in the use forms, prepared from these formulations, as a
mixture with synergistic agents. Synergistic agents are compounds
which increase the action of the active compounds, without it being
necessary for the synergistic agent added to be active itself.
The active compound content of the use forms prepared from the
commercially available formulations can vary within wide limits.
The active compound concentration of the use forms can be from
0.00001 to 100% by weight of active compound, preferably between
0.00004 and 1% by weight.
The compounds are employed in a customary manner appropiate for the
use forms.
When used against pests of stored products, the active compounds
are distinguished by an excellent residual action on wood and clay
as well as a good stability to alkali on limed substrates.
The following examples illustrate the present invention more
specifically. It should be understood, however, that the invention
is in no way limited to these examples alone.
(A) Biological Examples relating to novel active substance
combinations of (1) a nitromethylene derivative of formula (I) and
an insecticidal compound of group (2);
EXAMPLE 1
Cnaphalocrosis test
Preparation of a test chemical
Solvent: 3 parts by weight of xylol
Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl
ether
To prepare a formulation of active compounds, 1 part by weight of
the active compounds was mixed with the aforesaid amount of the
solvent containing the aforesaid amount of the emulsifier, and the
mixture was diluted to a predetermined concentration with
water.
Testing method
Three rice seedlings, 15 cm tall, were planted in each of vinyl
resin pots having a diameter of 9 cm. Ten days after the
plantation, a water dilution of the active compounds in a
predetermined concentration prepared as above was sprayed onto the
plants in an amount of 20 ml per pot by means of a spray gun. After
air drying the spray, a plastic net cylinder having a diameter of 9
cm and a height of 25 cm was put over each pot, and ten 4th instar
larvae of paddy leaf rollers (Cnaphalocrosis medinalis Gueneer)
were inoculated in each pot. The pots were each placed in a
constant temperature chamber, and two days later, the number of
dead insects was counted. The kill ratio was then calculated. The
above test was carried out through two replicates.
The results are shown in Table 1.
TABLE 1 ______________________________________ Cnaphalocrosis test
Concentration of the active ingredient Kill ratio Test chemical
(ppm) (%) ______________________________________ No. 1 + [A] 40 + 8
100 No. 1 + [B] 40 + 8 100 No. 2 + [A] 40 + 8 100 No. 2 + [B] 40 +
8 100 No. 3 + [A] 40 + 8 100 No. 3 + [B] 40 + 8 100 No. 4 + [A] 40
+ 8 100 No. 4 + [B] 40 + 8 100 No. 5 + [A] 40 + 8 100 No. 5 + [B]
40 + 8 100 No. 1 40 10 No. 2 40 15 No. 3 40 15 No. 4 40 20 No. 5 40
30 [A] 8 30 [B] 8 45 Non-treated -- 0
______________________________________ Note 1. None of the mixed
and single chemicals used in the tests of this example showed
phytotoxicity. 2. Compounds of general formula (I) used in this
invention: Compound No. 1:
1(2-methyl-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine.
Compound No. 2:
1(2-methoxy-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine.
Compound No. 3:
1(2-bromo-5-pyridylmethyl)-2-(nitro-methylene)tetrahydropyrimidine.
Compound No. 4:
1(2-chloro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine.
Compound No. 5:
1(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine. 3.
Compounds (according to group (2) insecticides mentioned above,
used i this invention: [A]: cartap [B]: thiocyclam
EXAMPLE 2
Sogatella test
Three rice plants, about 15 cm tall, were planted in each of pots
having a diameter of about 13 cm, and 10 days after the plantation,
a water dilution of the active compounds in a predetermined
concentration prepared as in Example 1 was sprayed onto the plants
in an amount of 20 ml per pot by means of a spray gun. Ten days and
20 days after the spraying, a cage was put over each pot, and ten
3rd instar larvae of white-backed planthopper (Sogatella furcifera)
were inoculated in each pot. The pots were each placed in a
constant temperature chamber, and 2 days and 7 days later, the
number of dead insects was counted. The kill ratio was then
calculated. The above test was carried out through two
replicates.
The results are shown in Table 2.
TABLE 2 ______________________________________ Sogatella test Kill
ratio (%) Concentration Inoculated Inoculated of the active 10 days
later 20 days later ingredient 2 days 7 days 2 days 7 days Test
chemical (ppm) later later later later
______________________________________ No. 1 + [A] 8 + 8 100 -- 90
100 4 + 4 65 100 20 80 No. 2 + [A] 8 + 8 100 -- 90 100 4 + 4 45 100
30 80 No. 3 + [A] 8 + 8 100 -- 100 -- 4 + 4 80 100 40 100 No. 4 +
[A] 8 + 8 100 -- 100 -- 4 + 4 90 100 40 100 No. 5 + [A] 8 + 8 100
-- 100 -- 4 + 4 100 -- 75 100 No. 1 8 30 40 10 10 No. 2 8 40 45 15
20 No. 3 8 80 80 30 30 No. 4 8 75 80 35 40 No. 5 8 90 90 35 35 [A]
8 0 85 0 70 Non-treated -- 0 0 0 0
______________________________________ Note 1. None of the mixed
and single chemicals used in Example 2 showed phytotoxicity. 2.
Compounds Nos. 1, 2, 3, 4 and 5 of general formula (I) used in this
invention are the same as those given in Example 1. 3. Compound
(according to group (2) insecticides mentioned above) used in this
invention. [A]: buprofezin
EXAMPLE 3
Plutella test
Testing method
A water dilution of the active compounds in a predetermined
concentration prepared as in example 1 was sprayed onto cabbage
seedlings before head formation, about 15 cm tall, planted in pots
having a diameter of cm in an amount of 20 ml per pot by means of
spray gun. The spray was air-dried, and ten 2nd instar larvae of
diamondback moth (Plutella maculipennis) were inoculated in each
pot. The pots were placed in a constant temperature chamber, and
the number of dead insects was counted 2 days and 7 days later. The
kill ratio was calculted. The test was carried out through two
replicates.
The results are shown in Table 3.
TABLE 3 ______________________________________ Plutella test
Concentration of the active Kill ratio (%) ingredient 2 days 7 days
Test chemical (ppm) later later
______________________________________ No. 1 + [A] 40 + 20 100 20 +
10 20 85 No. 1 + [B] 40 + 4 100 20 + 2 40 75 No. 2 - [A] 40 + 20
100 20 + 10 20 80 No. 2 + [B] 40 + 4 100 20 + 2 30 75 No. 3 + [A]
40 + 20 100 20 + 10 40 100 No. 3 + [B] 40 + 4 100 20 + 2 45 80 No.
4 + [A] 40 + 20 100 20 + 10 35 95 No. 4 + [B] 40 + 4 100 20 + 2 50
90 No. 5 + [A] 40 + 20 100 20 + 10 50 100 No. 5 + [B] 40 + 4 100 20
+ 2 70 100 No. 1 40 35 35 No. 2 40 30 30 No. 3 40 40 40 No. 4 40 40
45 No. 5 40 55 60 [A] 20 0 35 [B] 4 0 40 Non-treated -- 0 0
______________________________________ Note 1. None of the mixed
and single chemicals used in Example 3 showed phytotoxicity. 2.
Compounds Nos. 1, 2, 3, 4 and 5 of general formula (I) used in this
invention are the same compounds as in Example 1. 3. Compounds
(according to group (2) insecticides mentioned above) used i this
invention [A]: diflubenzuron [B]:
N--(2,6difluorobenzoyl)-N'[3,5dichloro-4-(3-chloro-5-trifluoromethyl-2-py
idyloxy)phenyl]urea
EXAMPLE 4
Plutella test
Testing method
A water dilution of the active compounds in a predetermined
concentration prepared as in Example 1 was sprayed onto cabbage
seedlings before head formation, about 15 cm tall, planted in pots
having a diameter of 9 cm in an amount of 20 ml per pot by means of
spray gun. After the spray was air-dried, ten 4th instar larvae of
organophosphorus-resistant diamondback moth (Plutella maculipennis)
were inoculated in each pot. The pots were each placed in a
constant temperature chamber. Two days later, the number of dead
insects was counted, and the kill ratio was calculated. The above
test was carried out through two replicates.
The results are shown in Table 4.
TABLE 4 ______________________________________ Plutella Test
Concentration of the active ingredient Kill ratio Test chemical
(ppm) (%) ______________________________________ No. 1 + [A] 40 +
40 100 No. 2 + [A] 40 + 40 100 No. 3 + [A] 40 + 40 100 No. 4 + [A]
40 + 40 100 No. 5 + [A] 40 + 40 100 No. 1 40 25 No. 2 40 20 No. 3
40 35 No. 4 40 35 No. 5 40 40 [A] 40 30 Non-treated -- 0
______________________________________ Note 1. None of the mixed
and single chemicals used in Example 4 showed phytotoxicity. 2.
Compounds Nos. 1, 2, 3, 4 and 5 of the general formula (I) are the
sam as those used in Example 1. 3. Compound (according to group (2)
insecticides mentioned above) used in this invention [A]:
3phenoxybenzyl 2(4-ethoxyphenyl)-2-methyl-propylether
EXAMPLE 5
Wettable powder
Twenty parts of active substance of the formula (I), 20 parts of
cartap, 55 parts of a 1:5 mixture of powdery diatomaceous earth and
powdery clay, 2 parts of alkylbenzenesulfonate and 3 parts of
sodium alkylnaphthalenesulfonate/formaldehyde condensate are
pulverized and mixed to form a wettable powder.
(B) Biological Examples relating to novel substance combinations of
(1) a nitromethylene derivative of formula (I) and a carboxylic
acid ester compound of group (3) (formula II):
EXAMPLE 6
Plutella test
Preparation of a test chemical
Solvent: 3 parts by weight of xylol
Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl
ether
To prepare a formulation of active compounds, 1 part by weight of
the active compouns were mixed with the aforesaid amount of the
solvent containing the aforesaid amount of the emulsifier, and the
mixture was diluted to a predetermined concentration with
water.
Testing method
A water dilution of the active compounds in a predetermined
concentration prepared as above was sprayed onto cabbage seedlings
before head formation, about 15 cm tall, planted in pots having a
diameter of 9 cm in an amount of 20 ml per pot by means of a spray
gun. The spray was air-dried, and ten 4th instar larvae of
organophosphorus resistant diamondback moth (Plutella maculipennis)
were inoculated in each pot. The pots were placed in a constant
temperature chamber, and the number of dead insects was counted 2
days later. The kill ratio was calculated. The test was carried out
through two replicates.
The results are shown in Table 5.
TABLE 5 ______________________________________ Plutella test
Concentration of the active ingredient Kill ratio Test chemical
(ppm) (%) ______________________________________ No. 1 + [B] 40 + 8
100 No. 1 + [E] 40 + 8 90 No. 1 + [G] 40 + 80 90 No. 2 + [A] 40 + 8
100 No. 2 + [C] 40 + 8 95 No. 2 + [F] 40 + 8 90 No. 3 + [B] 40 + 8
100 No. 3 + [C] 40 + 8 100 No. 3 + [G] 40 + 80 100 No. 4 + [A] 40 +
8 100 No. 4 + [D] 40 + 8 90 No. 4 + [E] 40 + 8 100 No. 5 + [D] 40 +
8 100 No. 5 + [E] 40 + 8 100 No. 5 + [F] 40 + 8 100 No. 1 40 25 No.
2 40 20 No. 3 40 35 No. 4 40 35 No. 5 40 40 [A] 8 30 [B] 8 30 [C] 8
20 [D] 8 5 [E] 8 20 [F] 8 15 [G] 80 25 Non-treated -- 0
______________________________________ Note 1. None of the mixed
and single chemicals used in the test of Example 1 showed
phytotoxicity. 2. Compounds of general formula (I) used in the
invention: Compound No. 1:
1(2-methyl-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine
Compound No. 2:
2(2-methoxy-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine
Compound No. 3:
1(2-bromo-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine
Compound No. 4:
1(2-chloro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine
Compound No. 5:
1(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine 3.
Compounds (carboxylic acid esters of formula (II) [A]: cyfluthrin
[B]: cyhalothrin [C]: fenpropathrin [D]: fenvalerate [E]:
flucythrinate [F]: fluvalinate [G]: cyano-5-phenoxybenzyl
1p-ethoxyphenyl-2,2-2,2-dichlorocyclopropane-1-carboxylate
EXAMPLE 7
(emulsifiable concentrate)
Two parts of active substance of the formula (I), two parts of
cyfluthrin, 81 parts of xylene, 8 parts by polyoxyethylene alkyl
phenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed
with stirring to form an emulsifiable concentrate.
(C) Biological Examples relating to novel substance combinations of
(1) a nitromethylene derivative of formula (I) and a carbamate of
group (4) (formula III):
EXAMPLE 8
Nilaparvata test
Preparation of a test chemical
Solvent: 3 parts by weight of xylol
Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl
ether
To prepare a formulation of active compounds, 1 part by weight of
the active compounds were mixed with the aforesaid amount of the
solvent containing the aforesaid amount of the emulsifier, and the
mixture was diluted to a predetermined concentration with
water.
Testing method
Three rice seedlings, 15 cm tall, were planted in each of pots
having a diameter of about 13 cm. Ten days after the plantation, a
water dilution of the active compounds in a predetermined
concentration prepared as above was sprayed onto the plants in an
amount of 20 ml per pot by means of a spray gun. After drying the
spray, a cage was put over each pot, and ten 4th instar larvae of
brown planthopper (Nilaparvata lugens) were inoculated in each pot.
The pots were each placed in a constant temperature chamber. Three
days later, the number of dead insects was counted, and the kill
ratio was calculated. The above test was carried out through two
replicates.
The results are shown in Table 6.
TABLE 6 ______________________________________ Nilaparvata test
Concentration of the active compo- Kill ratio Test chemical nents
(ppm) (%) ______________________________________ No. 1 + [A] 8 +
100 95 No. 1 + [H] 8 + 100 80 No. 2 + [D] 8 + 100 80 No. 2 + [I] 8
+ 100 85 No. 2 + [B] 8 + 100 100 No. 3 + [C] 8 + 100 90 No. 3 + [D]
8 + 100 90 No. 4 + [A] 8 + 100 100 No. 4 + [B] 8 + 100 100 No. 4 +
[F] 8 + 100 100 No. 5 + [B] 8 + 100 100 No. 5 + [E] 8 + 100 90 No.
5 + [G] 8 + 100 80 No. 1 8 10 No. 2 8 5 No. 3 8 15 No. 4 8 30 No. 5
8 35 [A] 100 50 [B] 100 45 [C] 100 10 [D] 100 15 [E] 100 20 [F] 100
50 [G] 100 5 [H] 100 15 [I] 100 35 Non-treated -- 0
______________________________________ Note 1. None of the mixed
and single chemicals used in the tests of this example showed
phytotoxicity. 2. Compounds of general formula (I) used in this
invention: Compound No. 1: tetrahydropyrimidine
ethyl)-2-(nitromethylene)-- Compound No. 2: tetrahydroprimidine
lmethyl)-2-(nitromethylene)-- Compound No. 3: tetrahydropyrimidine
thyl)-2-(nitromethylene)-- Compound No. 4:
1(2-chloro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine
Compound No. 5:
1(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine 3.
Compounds (carbamates of formula III) used in this invention [A]:
propoxur [B]: BPMC [C]: isoprocarb [D]: metolcarb [E]: xylylcarb
[F]: carbofuran [G]: carbosulfan [H]: aminosulfan [I]:
bendiocarb
EXAMPLE 9
Aphis test
Testing method
Cotton aphids (Aphis gossypii) which were bred were inoculated in
eggplants seedlings, about 15 cm tall, grown in pots having a
diameter of 9 cm at a rate of about 100 per seedlings. One day
after the inoculation, a water dilution in a predetermined
concentration of the active compounds prepared as in Example 8 was
sprayed by means of a spray gun at a rate of 20 ml per pot. After
the spraying, the pots were left to stand in a greenhouse kept at
28.degree. C. Two days after the spraying, the number of dead
insects was counted, and the kill ratio was calculated.
The results are shown in Table 7.
TABLE 7 ______________________________________ Aphis Test
Concentration of the active components Kill ratio Test chemical
(ppm) (%) ______________________________________ No. 1 + [A] 40 +
40 100 No. 1 + [B] 40 + 40 100 No. 2 + [A] 40 + 40 100 No. 2 + [B]
40 + 40 100 No. 3 + [A] 40 + 40 100 No. 3 + [B] 40 + 40 100 No. 4 +
[A] 40 + 40 100 No. 4 + [B] 40 + 40 100 No. 4 + [B] 40 + 40 100 No.
5 + [A] 40 + 40 100 No. 5 + [B] 40 + 40 100 No. 1 40 17 No. 2 40 22
No. 3 40 26 No. 4 40 41 No. 5 40 37 [A] 40 36 [B] 40 40 Non-treated
-- 0 ______________________________________ Note 1. None of the
mixed and single chemicals used in the tests of this example showed
phytotoxicity. 2. Compounds Nos. 1, 2, 3, 4 and 5 of general
formula (I) used in this invention are the same as those used in
Example 8. 3. Compounds (carbamates of formula III) used in the
invention [A]: ethiofencarb [B]: pirimicarb
EXAMPLE 10
(wettable powder)
Twenty parts of active substance of the formula (I), 20 parts of
propoxur, 55 parts of a 1:5 mixture of powdery diatomaceous earth
and powdery clay, 2 parts of sodium alkylbenzenesulfonate and 3
parts of sodium alkylbenzenesulfonate and 3 parts of sodium
alkylnaphthalene sulfonate/formaldehyde condensate are pulverized
and mixed to form a wettable powder.
EXAMPLE 11
(dust)
One part of active substance of the formula (I), one part of BPMC
and 98 parts of powdery clay are pulverized and mixed to form a
dust.
EXAMPLE 12
(granules)
Ninety-six parts of clay mineral particles having a particle size
distribution between 0.2 and 2 mm are put in a rotary mixer, and
with rotation, 2 parts of active substance of formula (I) and 2
parts of carbofuran and sprayed onto the particles to wet them
uniformly and the particles are dried to form granules.
(D) Biological Examples relating to novel substance combinations of
(1) a nitromethylene derivative of formula (I) and an
organophosphate ester of formula (IV):
EXAMPLE 13
Cnaphalocrocis test
Preparation of a test chemical
Solvent: 3 parts by weight of xylol
Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl
ether
To prepare a formulation of active compounds, 1 part by weight of
the active compounds were mixed with the aforesaid amount of the
solvent containing the aforesaid amount of the emulsifier, and the
mixture was diluted to a predetermined concentration with
water.
Testing method
Three rice seedlings, 15 cm tall, were planted in each of vinyl
resin pots having a diameter of 9 cm. Ten days after the
plantation, a water dilution of the active compounds in a
predetermined concentration prepared as above was sprayed onto the
plants in an amount of 20 ml per pot by means of a spray gun. After
air drying the spray, a plastic net cylinder having a diameter of 9
cm and a height of 25 cm was put over each pot, and ten 4th instar
larvae of paddy leaf roller (Cnaphalocrocis medinalis) were
inoculated in each pot. The pots were placed in a constant
temperature chamber. Two days later, the number of dead insects was
counted, and the kill ratio was then calculated. The above test was
carried out through two replicates.
The results are shown in Table 8.
TABLE 8 ______________________________________ Onaphalocrocis test
Concentration of the active components Kill ratio Test chemical
(ppm) (%) ______________________________________ No. 1 + [A] 40 + 8
100 No. 1 + [D] 40 + 8 90 No. 2 + [B] 40 + 8 90 No. 2 + [C] 40 + 8
100 No. 3 + [A] 40 + 8 100 No. 3 + [B] 40 + 8 100 No. 4 + [B] 40 +
8 100 No. 4 + [C] 40 + 8 100 No. 5 + [C] 40 + 8 100 No. 5 + [D] 40
+ 8 100 No. 1 40 10 No. 2 40 15 No. 3 40 15 No. 4 40 20 No. 5 40 30
[A] 8 40 [B] 8 30 [C] 8 50 [D] 8 30 Non-treated -- 0
______________________________________ Note 1. None of the mixed
and single chemicals used in the tests of this example showed
phytotoxicity. 2. Compounds of general formula (I) used in this
invention: Compound No. 1: tetrahydropyrimidine
ethyl)-2-(nitromethylene)-- Compound No. 2: tetrahydropyrimidine
methyl)-2-(nitromethylene)-- Compound No. 3: tetrahydropyrimidine
thyl)-2-(nitromethylene)-- Compound No. 4:
1(2-chloro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine
Compound No. 5:
1(2-fluoro-5-pyridylmethyl)-2-(nitromethylene)imidazolidine 3.
Compounds (organophosphate esters of formula IV) used in this
inventio [A]: isoxathin [B]: pyridaphenthion [C]: tetrachlorvinphos
[D]: sulprofos
EXAMPLE 14
Plutella test
Testing method
A water dilution of the active compounds in a predetermined
concentration prepared as in Example 13 was sprayed onto cabbage
seedlings before heading, about 15 cm tall and grown in pots having
a diameter of 9 cm, at a rate of 20 ml per pot. After air-drying
the sprayed chemical, ten 4th instar larvae of
organophosphate-resistant diamondback (Plutella maculipennis) moth
were inoculated per pot. The pots were placed in a
constant-temperature chamber. Two days later, the number of dead
insects was counted, and the kill ratio was calculated. The tst was
conducted through two replicates.
The results are shown in Table 9.
TABLE 9 ______________________________________ Plutella test
Concentration of the active compo- Kill ratio Test chemical nents
(ppm) (%) ______________________________________ No. 1 + [A] 40 +
40 100 No. 1 + [B] 40 + 40 100 No. 1 + [D] 40 + 40 100 No. 2 + [A]
40 + 40 100 No. 2 + [B] 40 + 40 100 No. 2 + [C] 40 + 40 100 No. 3 +
[A] 40 + 40 100 No. 3 + [B] 40 + 40 100 No. 3 + [C] 40 + 40 100 No.
4 + [B] 40 + 40 100 No. 4 + [C] 40 + 40 100 No. 4 + [D] 40 + 40 100
No. 5 + [A] 40 + 40 100 No. 5 + [C] 40 + 40 100 No. 5 + [D] 40 + 40
100 No. 1 40 25 No. 2 40 20 No. 3 40 35 No. 4 40 35 No. 5 40 40 [A]
40 25 [B] 40 40 [C] 40 30 [D] 40 30 Non-treated -- 0
______________________________________ Note 1. None of the mixed
and single chemicals used in the test of Example 14 showed
phytotoxicity. 2. Compounds Nos. 1, 2, 3, 4 and 5 of general
formula (I) used in the invention are the same as those used in
Example 13. 3. Compounds (organophosphate esters of formula IV)
used in the invention [A]: prothiofos [B]: pirimiphosmethyl [C]:
chlorpyrifos [D]: acephate
EXAMPLE 15
Myzus test
Testing method
Green peach aphids (Myzus persicae) having resistance to
organophosphates and carbamates were inoculated in eggplant
seedlings, about 20 cm tall and grown in pots having a diameter of
cm, at a rate of about 100 per seedling. One day after the
inoculation, a water dilution of the active compounds in a
predetermined concentration prepared as in Example 13 was sprayed
onto the plants at a rate of 20 ml per pot. After the spraying, the
pots were left to stand in a greenhouse kept at 28.degree. C. Three
days after the spraying, the number of dead insects was counted,
and the kill ratio was calculated.
The results are shown in Table 10.
TABLE 10 ______________________________________ Myzus test
Concentration of the active compo- Kill ratio Test chemical nents
(ppm) (%) ______________________________________ No. 1 + [A] 40 +
40 100 No. 1 + [B] 40 + 40 100 No. 2 + [A] 40 + 40 100 No. 2 + [B]
40 + 40 100 No. 3 + [A] 40 + 40 100 No. 3 + [B] 40 + 40 100 No. 4 +
[A] 40 + 40 100 No. 4 + [B] 40 + 40 100 No. 5 + [A] 40 + 40 100 No.
5 + [B] 40 + 40 100 No. 1 40 31 No. 2 40 25 No. 3 40 38 No. 4 40 30
No. 5 40 44 [A] 40 15 [B] 40 8 Non-treated -- 0
______________________________________ Note 1. None of the mixed
and single chemicals used in the test of Example 3 showed
phytotoxicity. 2. Compounds Nos. 1, 2, 3, 4 and 5 of general
formula (I) used in this invention are the same as those used in
Example 13. 3. Compounds (organophosphate esters of formula IV)
used in the invention [A]: disulfoton [B]: vamidothion
EXAMPLE 16
(wettable powder)
Twenty parts of active substance of the formula (I), 20 parts of
prothiofos, 55 parts of a 1:5 mixture of powdery diatomaceous earth
and powdery clay, 2 parts of sodium alkylbenzenesulfonate and 3
parts of sodium alkylnaphthalenesulfonate/formaldehyde condensate
are pulverized and mixed to form a wettable powder.
EXAMPLE 17
(dust)
One part of active substance of the formula (I), two parts of
pyridaphenthion and 97 parts of powdery clay are pulverized and
mixed to form a dust.
EXAMPLE 18
(granules)
Ninety-five parts of clay mineral particles having a particle size
distribution between 0.2 and 2 mm are put in a rotary mixer, and
with rotation, 2 parts of active substance of formula (I) and 3
parts of disulfoton are sprayed onto the particles to wet them
uniformly and the particles are dried to form granules.
It is understood that the specification and examples are
illustrative but not limitative of the present invention and that
other embodiments within the spirit and scope of the invention will
suggest themselves to those skilled in the art.
* * * * *